US11613720B2 - Aqueous composition and cleaning method using same - Google Patents

Aqueous composition and cleaning method using same Download PDF

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US11613720B2
US11613720B2 US17/049,828 US201917049828A US11613720B2 US 11613720 B2 US11613720 B2 US 11613720B2 US 201917049828 A US201917049828 A US 201917049828A US 11613720 B2 US11613720 B2 US 11613720B2
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acid
ester
phosphate
aqueous composition
salt
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US20210047593A1 (en
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Toshiyuki Oie
Akinobu HORITA
Takahiro KIKUNAGA
Kenji Yamada
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Mitsubishi Gas Chemical Co Inc
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    • C11D11/0047—
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
    • H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the present invention relates to an aqueous composition and a cleaning method using the same, for example, a cleaning composition used in a production process of an electronic device (for example, a semiconductor element) and a cleaning method using the same.
  • a dry etching process is usually employed upon forming a semiconductor integrated circuit.
  • dry etch residues a zirconium-based residue, a titanium-based residue, a polymer residue, etc.
  • a cleaning agent used for removing such dry etch residues does not adversely affect (for example, corrode) the metal line material (for example, copper, titanium, cobalt, tungsten, etc.) used in the semiconductor integrated circuit to be cleaned.
  • cleaning agents have been developed from these points of view.
  • cleaning compositions for removing dry etch residues remaining after dry etching, cleaning methods using the same, and the like are disclosed in Japanese Unexamined Patent Application Publication (translation of PCT) No. 2013-533631 (Patent document 1), Japanese Unexamined Patent Application Publication No. 2016-171294 (Patent document 2), Japanese Unexamined Patent Application Publication No. 2006-83376 (Patent document 3) and else.
  • a hardmask is sometimes used during the process of forming a semiconductor integrated circuit. While silicon- and titanium-based materials have been conventionally employed as the materials of such hardmasks, zirconia-based hardmasks have recently been proposed as well (Non-patent document 1: M Padmanaban et al, J. Photopolym. Sci. Technol., 27 (2014) 503).
  • alumina-based etch stop layers are recently proposed (Non-patent document 2: 16th MME workshop, Goeteborg, Sweden, 2005 “Etch stop materials for release by vapor HF etching”).
  • the present invention provides an aqueous composition, a cleaning method using the same and the like below.
  • An aqueous composition comprising:
  • composition according to [4] wherein Component (A) is hexafluorosilicic acid or a salt thereof (for example, an ammonium salt).
  • composition according to any one of [1]-[4] above, wherein the aqueous composition comprises at least one selected from:
  • n-butylphosphonic acid n-pentylphosphonic acid, n-hexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, n-nonylphosphonic acid, n-decylphosphonic acid, n-undecylphosphonic acid, n-dodecylphosphonic acid, n-tridecylphosphonic acid or a mixture thereof, as the alkylphosphonic acid;
  • n-butylphosphonate ester n-pentylphosphonate ester, n-hexylphosphonate ester, n-heptylphosphonate ester, n-octylphosphonate ester, n-nonylphosphonate ester, n-decylphosphonate ester, n-undecylphosphonate ester, n-dodecylphosphonate ester, n-tridecylphosphonate ester or a mixture thereof, as the alkylphosphonate ester; and
  • alkylphosphonic acid is a C 4-13 alkylphosphonic acid (preferably a C 5-11 alkylphosphonic acid, more preferably a C 5-9 alkylphosphonic acid, and still more preferably a C 6-8 alkylphosphonic acid).
  • composition according to any one of [1]-[4] above, wherein the aqueous composition comprises at least one selected from:
  • n-butyl phosphate n-pentyl phosphate, n-hexyl phosphate, n-heptyl phosphate, n-octyl phosphate, n-nonyl phosphate, n-decyl phosphate, n-undecyl phosphate, n-dodecyl phosphate, n-tridecyl phosphate, 2-ethylhexyl phosphate, isodecyl phosphate or a mixture thereof, as the alkyl phosphate; and
  • alkyl phosphate is a C 4-13 alkyl phosphate (preferably a C 5-11 alkyl phosphate, more preferably a C 5-9 alkyl phosphate, and still more preferably a C 6-8 alkyl phosphate).
  • composition according to any one of [1]-[6a] above which is a dry etch residue removing composition used for removing a residue remaining after dry etching (for example, a zirconia-based dry etch residue).
  • composition according to any one of [1]-[6b] above which is a composition for preventing corrosion of a line material (for example, cobalt, a cobalt alloy or the like) of an electronic device targeted for cleaning.
  • a line material for example, cobalt, a cobalt alloy or the like
  • a method for cleaning an electronic device comprising the step of bringing the composition according to any one of [1]-[8] above into contact with the electronic device.
  • a method for producing an electronic device comprising the step of bringing the composition according to any one of [1]-[8] above into contact with the electronic device.
  • a cleaning solution comprising the composition according to any one of [1]-[8] above.
  • An aqueous composition in a preferred aspect of the present invention is capable of efficiently removing dry etch residues (for example, a zirconium-based dry etch residue, a titanium-based dry etch residue, a polymer-based dry etch residue, etc.) while preventing corrosion of a metal line material such as cobalt or a cobalt alloy, silicon nitride, an interlayer insulating film and the like.
  • dry etch residues for example, a zirconium-based dry etch residue, a titanium-based dry etch residue, a polymer-based dry etch residue, etc.
  • a cleaning method in a preferred aspect of the present invention has a favorable effect of preventing corrosion of a line material such as cobalt or a cobalt alloy, silicon nitride, an interlayer insulating film and the like, and has a favorable effect of removing dry etch residues, it allows production of a high precision, high quality electronic device such as a semiconductor element at high yield in a production process of said electronic device.
  • FIG. 1 A cross-sectional schematic view of a semiconductor element of one embodiment before removing dry etch residue 1 , the element comprising a structure including a zirconia-based hardmask 2 , cobalt or a cobalt alloy 3 , a low dielectric interlayer insulating film 5 and silicon nitride 6 .
  • FIG. 2 A cross-sectional schematic view of a semiconductor element of one embodiment before removing dry etch residue 1 , the element comprising cobalt or a cobalt alloy at the bottom of the via and a structure including a zirconia-based hardmask 2 , cobalt or a cobalt alloy 3 , alumina 4 , a low dielectric interlayer insulating film 5 and silicon nitride 6 .
  • FIG. 3 A cross-sectional schematic view of a semiconductor element of one embodiment before removing dry etch residue 1 , the element comprising alumina at the bottom of the via and a structure including a zirconia-based hardmask 2 , cobalt or a cobalt alloy 3 , alumina 4 , a low dielectric interlayer insulating film 5 and silicon nitride 6 .
  • An aqueous composition of the present invention comprises:
  • ranges indicating the contents of respective components are inclusive of the upper and lower values.
  • the above-mentioned range of the content of Component (A) is inclusive of 0.001 mass % and 20 mass %.
  • a fluorine-containing compound used in the present invention is selected from tetrafluoroboric acid, hexafluorosilicic acid, hexafluoroaluminic acid, hexafluorotitanic acid and a salt thereof.
  • salts of these compounds include an ammonium salt, a tetramethylammonium salt, a tetraethylammonium salt, a tetrapropylammonium salt, a tetrabutylammonium salt, a lithium salt, a sodium salt, a potassium salt, a rubidium salt, a cesium salt, a beryllium salt, a magnesium salt, a strontium salt, a barium salt and the like.
  • hexafluorosilicic acid or a salt thereof is particularly preferable.
  • the amount of the fluorine-containing compound contained in the composition is 0.001-20 mass %, preferably 0.005-10 mass %, more preferably 0.01-5 mass % and particularly preferably 0.03-2 mass % with respect to the total amount of the composition.
  • hydrogen fluoride, ammonium fluoride or the like can also be added as appropriate in addition to the above-mentioned fluorine-containing compounds.
  • amount to be added can suitably be determined considering the amounts of other components added, it is, for example, 0.001-10 mass %, preferably 0.005-1 mass % and more preferably 0.01-0.1 mass % with respect to the total amount of the composition.
  • An alkylphosphonic acid used in the present invention is a C 4-13 alkylphosphonic acid having 4-13 carbon atoms (an alkylphosphonic acid having 4-13 carbon atoms).
  • alkylphosphonic acids are known and commercially available (for example, available from Tokyo Chemical Industry Co., Ltd.).
  • the alkylphosphonic acid is preferably a C 5-11 alkylphosphonic acid, more preferably a C 5-9 alkylphosphonic acid, and still more preferably a C 6-8 alkylphosphonic acid.
  • the alkyl moiety of the alkylphosphonic acid may be either linear or branched, it is preferably linear. If the alkyl moiety of the alkylphosphonic acid is branched, the number of the branched chains is preferably 5 or less, more preferably 3 or less, and particularly preferably 1.
  • an ester of the above-described alkylphosphonic acid may also be used.
  • an alkyl ester of the above-described C 4-13 alkylphosphonic acid (an alkylphosphonic acid having 4-13 carbon atoms) may also be used.
  • an alkylphosphonic acid can usually be represented by general formula R 1 P( ⁇ O)(OH) 2 (wherein, R 1 is an alkyl group)
  • an alkylphosphonate ester represented by general formula R 1 P( ⁇ O)(OR 2 ) 2 (wherein, R 1 is an alkyl group, and R 2 is an alkyl group or hydrogen: provided that at least one of the two R 2 is an alkyl group) can also be used in the aqueous composition.
  • an alkylphosphonate ester as described herein also comprises an alkyl ester of a phosphonic acid (phosphonate ester).
  • a phosphonate ester represented by general formula R 1 P( ⁇ O)(OR 2 ) 2 (wherein, R 1 is hydrogen, R 2 is an alkyl group or a hydrogen atom: provided that at least one of the two R 2 is an alkyl group) can also be used herein as the alkylphosphonate ester in the aqueous composition.
  • R 1 and R 2 are each independently an alkyl group or a hydrogen atom: provided that at least one among R 1 and the two R 2 is an alkyl group).
  • the alkylphosphonate ester used in the present invention is a C 4-13 alkylphosphonate ester having a total of 4-13 carbon atoms (an alkylphosphonate ester having a total of 4-13 carbon atoms).
  • the alkylphosphonate ester is preferably a C 5-11 alkylphosphonate ester, more preferably a C 5-9 alkylphosphonate ester and still more preferably a C 6-8 alkylphosphonate ester.
  • the alkyl chains of R 1 and R 2 in General formula (A) above each independently have carbon atoms of preferably 4-12, more preferably 6-11 and still more preferably 8-10.
  • alkyl groups of the alkylphosphonate ester may be either linear or branched, they preferably contain linear alkyl groups.
  • the number of alkyl chains in General formula (A) above namely, the total number of the alkyl chains of R 1 and R 2 , is preferably 2 or less.
  • an alkylphosphonate ester in which both of R 1 and R 2 in General formula (A) R 1 P( ⁇ O)(OR 2 ) 2 above are alkyl groups can be used, an alkylphosphonate ester in which R 1 is an alkyl group while one or none of R 2 is an alkyl group, an alkylphosphonate ester in which R 1 is hydrogen while two or less of R 2 is an alkyl group, or the like may be used.
  • an alkylphosphonic acid having only a single alkyl chain that is, only one among R 1 and the two R 2 of General formula (A) R 1 P( ⁇ O)(OR 2 ) 2 above is an alkyl group
  • R 1 P( ⁇ O)(OR 2 ) 2 above is an alkyl group
  • an alkylphosphonate ester in which only R 1 in General formula (A) above is an alkyl group is used.
  • the salt of the alkylphosphonic acid used in the present invention is a salt of the above-described alkylphosphonic acid, which is, for example, an ammonium salt, a tetramethylammonium salt, a tetraethylammonium salt, a tetrapropylammonium salt, a tetrabutylammonium salt, a lithium salt, a sodium salt, a potassium salt, a rubidium salt, a cesium salt, a beryllium salt, a magnesium salt, a calcium salt, a strontium salt, a barium salt or the like.
  • an ammonium salt a tetramethylammonium salt, a tetraethylammonium salt, a tetrapropylammonium salt, a tetrabutylammonium salt, a lithium salt, a sodium salt, a potassium salt, a rubidium salt, a cesium salt, a be
  • alkylphosphonic acid or a salt thereof used in the present invention examples include n-butylphosphonic acid, n-pentylphosphonic acid, n-hexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, n-nonylphosphonic acid, n-decylphosphonic acid, n-undecylphosphonic acid, n-dodecylphosphonic acid, n-tridecylphosphonic acid, a salt thereof or a mixture thereof.
  • alkylphosphonic acid or a salt thereof that can be used include n-pentylphosphonic acid, n-hexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, n-nonylphosphonic acid, n-decylphosphonic acid, n-undecylphosphonic acid, a salt thereof and a mixture thereof.
  • a salt of the above-described alkylphosphonate ester can also be used in the aqueous composition.
  • the salt of the alkylphosphonate ester include those corresponding to salts of the above-described alkylphosphonic acids.
  • the concentration of the alkylphosphonic acid, the alkylphosphonate ester or the salt thereof in the aqueous composition can suitably be changed by considering the kind of the line material of the electronic device targeted for etching or cleaning and the kind of the masking material used in the etching step.
  • the concentration of the alkylphosphonic acid, the alkylphosphonate ester or the salt thereof is preferably 0.0002-2 mass %, more preferably 0.0003-0.5 mass % and particularly preferably 0.0003-0.1 mass % with respect to the total amount of the composition.
  • An alkyl phosphate used in the present invention is a C 4-13 alkyl phosphate having 4-13 carbon atoms (an alkyl phosphate having 4-13 carbon atoms).
  • alkyl phosphates are known and commercially available (for example, available from Tokyo Chemical Industry Co., Ltd.).
  • the alkyl phosphate is preferably a C 5-11 alkyl phosphate, more preferably a C 5-9 alkyl phosphate, and still more preferably a C 6-8 alkyl phosphate.
  • the alkyl moiety of the alkyl phosphate may be either linear or branched, it is preferably linear. In a branched alkyl moiety of the alkyl phosphate, the number of the branched chains is preferably 5 or less, more preferably 3 or less, and particularly preferably 1.
  • a dialkyl ester or a trialkyl ester of phosphoric acid may also be used as the alkyl phosphate in the aqueous composition of the present invention.
  • a monoalkyl ester of phosphoric acid represented by General formula P( ⁇ O)(OR 3 ) 3 (wherein, all of R 3 are hydrogen atoms) in which only one of R 3 is substituted with an alkyl group, but also a dialkyl ester in which two of R 3 are substituted with alkyl groups and a trialkyl ester in which all of R 3 are substituted with alkyl groups can be used in the aqueous composition of the present invention.
  • the alkyl phosphate is preferably a dialkyl ester in which the number of alkyl chains is two or less (i.e., two of R 3 in General formula P( ⁇ O)(OR 3 ) 3 above are alkyl groups) or a monoalkyl ester (i.e., only one of R 3 in General formula P( ⁇ O)(OR 3 ) 3 above is an alkyl group), and more preferably a monoalkyl ester in which the number of the alkyl chain is 1.
  • the alkyl phosphate preferably has a single alkyl chain (an alkyl group represented by R 3 above).
  • the alkyl phosphate has a total of 4-13 carbon atoms. Regardless of the number of ester bonds, the alkyl phosphate is preferably a C 5-11 alkyl phosphate ester, more preferably a C 5-9 alkyl phosphate ester and still more preferably a C 6-8 alkyl phosphate ester.
  • the alkyl chain of R 3 in General formula P( ⁇ O)(OR 3 ) 3 above has carbon atoms of preferably 4-12, more preferably 6-11 and still more preferably 8-10. While the alkyl groups of the alkyl phosphate, namely, R 3 in General formula P( ⁇ O)(OR 3 ) 3 above, may be either linear or branched, they are preferably linear.
  • the salt of the alkyl phosphate used in the present invention is a salt of the above-described monoalkyl ester or dialkyl ester of phosphoric acid, which is, for example, an ammonium salt, a tetramethylammonium salt, a tetraethylammonium salt, a tetrapropylammonium salt, a tetrabutylammonium salt, a lithium salt, a sodium salt, a potassium salt, a rubidium salt, a cesium salt, a beryllium salt, a magnesium salt, a calcium salt, a strontium salt, a barium salt or the like.
  • alkyl phosphate or a salt thereof used in the present invention examples include n-butyl phosphate, n-pentyl phosphate, n-hexyl phosphate, n-heptyl phosphate, n-octyl phosphate, n-nonyl phosphate, n-decyl phosphate, n-undecyl phosphate, n-dodecyl phosphate, n-tridecyl phosphate, 2-ethylhexyl phosphate, isodecyl phosphate, a salt thereof or a mixture thereof.
  • alkyl phosphate or a salt thereof examples include n-pentyl phosphate, n-hexyl phosphate, n-heptyl phosphate, n-octyl phosphate, n-nonyl phosphate, n-decyl phosphate, n-undecyl phosphate, 2-ethylhexyl phosphate, isodecyl phosphate, a salt thereof and a mixture thereof.
  • the concentration of the alkyl phosphate or a salt thereof in the aqueous composition can suitably be changed by considering the kind of the line material of the electronic device targeted for etching or cleaning and the kind of the masking material used in the etching step.
  • the concentration of the alkyl phosphate or a salt thereof is in a range of preferably 0.0002-2 mass %, still more preferably 0.0003-0.5 mass % and particularly preferably 0.0003-0.1 mass % with respect to the total amount of the composition.
  • the composition of the present invention is aqueous and contains water as a diluent. While the water of the present invention is not particularly limited, it is preferably water that has been removed of metal ions, organic impurities, particles and the like by distillation, an ion exchange treatment, a filter treatment, any adsorption treatment or the like, and is particularly preferably pure water or ultrapure water.
  • the amount of water contained in the composition is usually 40-99.9999 mass % and preferably, 97.95-99.9697 mass %.
  • aqueous composition of the present invention may be added with an additive that is conventionally used in aqueous compositions for semiconductors as long as it does not interfere with the purpose of the present invention.
  • the aqueous composition of the present invention may be added with an additive that is conventionally used in aqueous compositions for semiconductors as long as it does not interfere with the purpose of the present invention.
  • an acid, alkali, a chelating agent, a surfactant, a defoamer, an oxidant, a reductant, an anti-corrosive agent for metals, a water-soluble organic solvent or the like may be added as additives.
  • additives are known and described, for example, in Japanese Unexamined Patent Application Publication (translation of PCT) No. 2013-533631.
  • the aqueous composition (liquid composition) of the present invention can be prepared by agitating the above-described Component (A), the above-described Component (B), water and the above-described other components, until homogeneous.
  • the range of the pH of the aqueous composition is not particularly limited, it is usually 0-7, preferably 0-6, more preferably 0-5 and still more preferably 0-4.
  • An aqueous composition in a preferred aspect of the present invention is capable of efficiently removing dry etch residues (for example, a zirconium-based dry etch residue, a titanium-based dry etch residue, a polymer-based dry etch residue, etc.) while preventing corrosion of a metal line material such as cobalt or a cobalt alloy, silicon nitride, an interlayer insulating film and the like.
  • dry etch residues for example, a zirconium-based dry etch residue, a titanium-based dry etch residue, a polymer-based dry etch residue, etc.
  • an aqueous composition of the present invention can remove dry etch residues by making contact with an electronic device (for example, a semiconductor element) in a wet etching step (or in a step prior to or following said step).
  • an electronic device for example, a semiconductor element
  • a cleaning solution may be placed in a cleaning container so that an electronic device targeted for cleaning can be immersed in the cleaning solution to remove the dry etch residues, thereby cleaning the electronic device.
  • an electronic device can be subjected to a treatment in a single-wafer cleaning mode to remove the dry etch residues, thereby cleaning the electronic device.
  • the aqueous cleaning composition can also favorably be used as an etching solution.
  • the aqueous composition can also be used as a cleaning solution for cleaning the electronic device after a step of chemical-mechanical polishing (CMP).
  • CMP chemical-mechanical polishing
  • an aqueous composition of the present invention may favorably be used in a cleaning method that comprises a step of cleaning an electronic device, and a method for producing an electronic device comprising such step.
  • the temperature of the cleaning solution of the present invention upon use is usually 10-80° C., preferably 15-70° C., more preferably 20° C.-65° C. and particularly preferably 20° C.-60° C.
  • the temperature may suitably be selected according to the conditions of cleaning and the electronic device used (for example, a semiconductor element).
  • the cleaning solution of the present invention is usually used for 0.2-60 minutes.
  • the time may suitably be selected according to the conditions of cleaning and the electronic device used (for example, a semiconductor element).
  • a rinse solution used following the cleaning solution of the present invention may be an organic solvent, water, carbonated water or ammonia water.
  • An electronic device targeted for cleaning and production employing the present invention is, for example, a semiconductor element or a display element, where a target for cleaning is usually an intermediate product that is obtained after a dry etching process.
  • a semiconductor element or a display element is a substrate material such as silicon, amorphous silicon, polysilicon or glass, an insulating material such as silicon oxide, silicon nitride, silicon carbide or a derivative thereof, a material such as cobalt, a cobalt alloy, tungsten or titanium-tungsten, a compound semiconductor such as gallium-arsenic, gallium-phosphorus, indium-phosphorus, indium-gallium-arsenic or indium-aluminum-arsenic, or an oxide semiconductor such as chromium oxide.
  • the electronic device targeted for cleaning by the present invention is particularly preferably an element using a cobalt or cobalt alloy line material, a zirconia-based hardmask, silicon nitride (SiN) and a low dielectric interlayer insulating film (for example, a tetraethoxysilicate film).
  • Dry etch residues targeted by the present invention are, for example, those that are generated upon forming a via or trench structure in a low dielectric interlayer insulating film by dry etching using a zirconia-based hardmask as a mask. Some of the dry etch residues are generated when etching gas makes contact with the zirconia-based hardmask. In this case, naturally, the targeted dry etch residue contains zirconium.
  • % refers to “mass %”.
  • Silicon nitride, an interlayer insulating film, silicon nitride, zirconia and a photoresist were sequentially formed from the bottom into a film, and then a photoresist was patterned thereon.
  • the predetermined part of the hardmask was removed by dry etching using the photoresist as a mask, and the photoresist was removed by oxygen plasma ashing. Furthermore, a via was formed in the silicon nitride and the interlayer insulating film by dry etching using the hardmask as a mask.
  • ⁇ Filmed Wafer> Wafer for Evaluating Damage to Silicon Nitride, Low Dielectric Interlayer Insulating Film and Cobalt
  • Wafers on which materials (silicon nitride, low dielectric interlayer insulating film and cobalt) were formed to give respective films were used.
  • TEOS tetraethoxysilicate
  • i.e., one kind of low dielectric interlayer insulating film was applied as the low dielectric interlayer insulating film.
  • TEOS formed into a film to a thickness of 1000 ⁇ on Si by chemical vapor deposition.
  • Cobalt formed into a film to a thickness of 2000 ⁇ on Si by physical vapor deposition.
  • Evaluation wafers A that were treated with various aqueous compositions (cleaning solutions) were observed by SEM.
  • the film thicknesses of the filmed wafers were measured using a x-ray fluorescence spectrometer SEA1200VX available from SII NanoTechnology (Film thickness measuring instrument A) or an optical film thickness gauge n&k 1280 available from n&k technology, Inc (Film thickness measuring instrument B).
  • the film thickness of the cobalt-filmed wafer was measured using Film thickness measuring instrument A while the film thicknesses of the silicon nitride- and TEOS-filmed wafers were measured using Film thickness measuring instrument B.
  • Each of the filmed wafers was treated with a cleaning solution, and the difference in the film thicknesses before and after the treatment was divided by the treatment time to determine E.R.
  • E.R. of 2 ⁇ /min or less for silicon nitride, E.R. of 5 ⁇ /min or less for TEOS and E.R. of 5 ⁇ /min or less for cobalt were found to be acceptable.
  • the pH value of the aqueous composition in each of the examples and the comparative examples was measured at 25° C. using a pH meter (pH meter F-52 available from Horiba, Ltd.).
  • Evaluation wafer A and the silicon nitride-, TEOS- and cobalt-filmed wafers were used for the test.
  • the wafers were immersed in the aqueous compositions (cleaning solutions) indicated in Table 1 at the treatment temperature indicated in Table 1, and subsequently rinsed with ultrapure water and dried by dry nitrogen gas blowing.
  • Evaluation wafers A were all subjected to the immersion treatment for 3 minutes, and the treated wafers were observed by SEM.
  • the silicon nitride-, TEOS- and cobalt-filmed wafers were each subjected to the immersion treatment for 30 minutes. E.R. was calculated from the film thicknesses before and after the treatment.
  • Example 1-14 the dry etch residues were found to be removed completely while preventing damage to silicon nitride (SiN), TEOS and cobalt.
  • the aqueous composition in a preferred aspect of the present invention is capable of efficiently removing dry etch residues while preventing corrosion of a metal line material such as cobalt or a cobalt alloy, silicon nitride, an interlayer insulating film and the like.
  • an etching solution, a cleaning solution and a cleaning method in a preferred aspect of the present invention have a favorable effect in preventing corrosion of a metal line material such as cobalt and a cobalt alloy, silicon nitride, an interlayer insulating film and the like and have a favorable effect in removing dry etch residues, they allow production of a high precision, high quality electronic device such as a semiconductor element at high yield in a production process of said electronic device.
  • SiN Silicon nitride

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